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Process for preparing (E2,Z6)-2,6-nonadienal

a technology of nonadienal and process, which is applied in the field of process for preparing (e2, z6)2, 6nonadienal, can solve the problems of high cost, high cost, and high cost of wittig reaction, and achieves the effects of industrially, economically and efficiently preparing

Active Publication Date: 2020-08-04
SHIN ETSU CHEM IND CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

The present invention is about a method for making a compound called (E2,Z6)-2,6-nonadienal, which is useful for making another compound called (E2)-cis-6,7-epoxy-2-nonenal, which is a pheromone used by red-necked longhombeetle. The method involves using a sulfoxide compound, a sulfur trioxide complex, and an amine compound to oxidize (Z3,Z6)-3,6-nonadien-1-ol, which is a widely available flavor compound. The invention allows for efficient, industrial, and economic production of (E2,Z6)-2,6-nonadienal.

Problems solved by technology

However, the process reported in Non-Patent Literature 1 has a problem that the process takes many manufacturing steps and the selectivity in the ethylation step is low.
The process reported in Non-Patent Literature 2 has a problem that the yield in the Wittig reaction is extremely low.
The process reported in Non-Patent Literature 3 has a problem that 1-methyl-1,5,7-triazabicyclo[4.4.0]decene is required as a base in a step of preparing a reagent used in the Wittig reaction and, however, this base is difficult to industrially obtain in a large amount.
The process reported in Non-Patent Literature 4 has a problem that ozonolysis is difficult to industrially carry out.
As described above, the conventional processes have many problems, and mass production in an industrial and economical manner has been impossible.

Method used

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  • Process for preparing (E2,Z6)-2,6-nonadienal

Examples

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example 1

on of (E2,Z6)-2,6-nonadienal (4)

[0068]Air in a reactor equipped with a stirrer, a condenser, and a thermometer was purged with nitrogen. Then, to the reactor were added (Z3,Z6)-3,6-nonadien-1-ol (1) (140.22 g, 1.0 mol), triethylamine (505.95 g, 5.0 mol), and methylene chloride (5000.0 g) and the temperature was maintained at from 20° C. to 25° C. A solution of a sulfur trioxide pyridine complex (477.48 g, 3.0 mol) in dimethylsulfoxide (2968.9 g, 38.0 mol) was added dropwise to the resulting reaction mixture at from 25° C. to 28° C. over 2 hours and stirred for 5 hours. Then, the mixture was cooled to 0° C. and an aqueous 5.0 wt % hydrochloric acid (3000.0 g) was added while preventing the temperature of the mixture from exceeding 25° C. Then, the resulting mixture was separated into layers and the aqueous layer was removed. The organic layer thus obtained was washed successively with water (2400.0 g), an aqueous 5.0 wt % sodium hydrogencarbonate solution (2500.0 g) and an aqueous 10...

reference example 1

-cis-6,7-epoxy-2-nonenal (5)

[0074]Air in a reactor equipped with a stirrer, a condenser, and a thermometer was purged with nitrogen. Then, to the reactor were added (E2,Z6)-2,6-nonadienal (4) (138.21 g, 1.0 mol) obtained in Example 1 and methylene chloride (3000.0 g), and the resulting mixture was cooled to −5° C. To the resulting mixture was added an aqueous 30 wt % hydrous metachloroperbenzoic acid (308.2 g, 1.25 mol) at from −5° C. to 0° C. over 3 hours, followed by stirring at from 0° C. to 5° C. for 10 hours. Next, precipitated crystals were filtered off and the filtrate was washed successively with an aqueous 10.0 wt % sodium thiosulfate solution (2000.0 g), an aqueous 2.0 wt % / o sodium hydroxide solution (2000.0 g), and an aqueous 20.0 wt % sodium chloride solution (2000.0 g). The solvent in the organic layer thus obtained was removed under a reduced pressure. The resulting concentrate was subjected to distillation for purification to obtain (E2)-cis-6,7-epoxy-2-nonenal (5) (...

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Abstract

The object of the present invention is to provide an industrial and economical process for preparing (E2,Z6)-2,6-nonadienal of the following formula (4):The present invention provides a process for preparing (E2,Z6)-2,6-nonadienal (4), comprising at least steps of:subjecting (Z3,Z6)-3,6-nonadien-1-ol of the following formula (1):to oxidation with a sulfoxide compound of the following formula (2):CH3(R1)S═O  (2)in which R1 represents a monovalent hydrocarbon group having from 1 to 12 carbon atoms,in the presence of a sulfur trioxide complex and an amine compound of the following formula (3):N(R2)(R3)(R4)  (3)in which R2, R3, and R4 each independently represent a monovalent hydrocarbon group having from 1 to 12 carbon atoms, or R3 and R4 may be bonded to each other to form a divalent hydrocarbon group having from 3 to 12 carbon atoms, R3-R4,to form the aforesaid (E2,Z6)-2,6-nonadienal (4).

Description

CROSS-REFERENCE TO RELATED APPLICATION[0001]This U.S. nonprovisional application claims priority to Japanese Application No. 2018-155251 filed Aug. 22, 2018, the entire contents of which are incorporated herein by reference.TECHNICAL FIELD[0002]The present invention relates to a process for preparing (E2,Z6)-2,6-nonadienal.BACKGROUND ART[0003](E2,Z6)-2,6-nonadienal is known as a useful intermediate for preparing (E2)-cis-6,7-epoxy-2-nonenal which is an aggregation pheromone of red-necked longhorn beetle (scientific name: Aromia bungii) known as a pest against Rosaceae trees such as cherry, Japanese apricot, peach, and plum (Non-Patent Literature 1 mentioned below). There is a need to establish an industrial and economical process for preparing the aforesaid intermediate, (E2,Z6)-2,6-nonadienal, in order to develop a new technology for preventing red-necked longhorn beetle, using an aggregation pheromone of the red-necked longhorn beetle.[0004]The following processes have been report...

Claims

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Application Information

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Patent Type & Authority Patents(United States)
IPC IPC(8): C07C45/29C07C47/21
CPCC07C45/29C07B2200/09C07C47/21C07D301/14C07D303/32A01N43/20
Inventor YAMASHITA, MIYOSHIMIYAKE, YUKIKINSHO, TAKESHI
Owner SHIN ETSU CHEM IND CO LTD